3 - alkenyl - 2,4 - dioxaspiro - (5:5) - 9:10 epoxy - undecanes and 8:11 methylene derivatives thereof



United States Patent 3,539,591 3 ALKENYL 2,4 DIOXASPIRO (5:5) 9:10

EPOXY UNDECANES AND 8:11 METHYL- ENE DERIVATIVES THEREOF Hans Batzer,Arlesheim, Otto Ernst, Pfelfingen, and Daniel Porret, Basel,Switzerland, assignors to Ciba Limited, Basel, Switzerland, a company ofSwitzerland No Drawing. Filed Oct. 21, 1960, Ser. No. 63,956 Claimspriority, application Switzerland, Oct. 23, 1959, 79,779/59 Int. Cl.C07d 15/04 US. Cl. 260-340.7 7 Claims The present invention provides newmonoepoxides of the formula in which R to R each represents a monovalentsubstituent such as a halogen atom or an alkoxy group or an aliphatic,cycloaliphatic, araliphatic or aromatic hydrocarbon radical, preferablyan alkyl radical containing 1 to 4 carbon atoms, or a hydrogen atom,where R and R together may also form a divalent substituent, such as amethylene group, and in which X and X represent hydrogen atoms or methylgroups.

To obtain the monoepoxides of the invention unsaturated acetals of thegeneral formula (III) As aldehydes of the Formula HI there may bementioned acrolein, methacrolein and crotonic aldehyde.

Suitable dialcohols of the Formula IV are, for example:

1 l-bis- ['hydroxymethyl] -cyclohexene- (3 l-bis- [hydroxymethyl]-6-methylcyclohexene- (3 :1 bis [hydroxymethyl] 2:4:6trimethylcyclohexcue-(3),

:1bis-[hydroxymethyl] 2:5 endomethylenecyclohexcue-(3), and

: l-bis- [hydroxymethyl] -4-chlorocyclohexene- (3 "ice The acetalisationcan be performed in known manner, for example by heating an aldehyde ofthe Formula III with a dialcohol of the Formula IV in the presence of anacid catalyst, such, for example, as sulfuric acid, phosphoric acid orpara-toluenesulfonic acid. In the process of the invention the acetalsof the Formula II are treated with an epoxidising agent, the reactionconditions being selected so that only the carbon-to-carbon double bondin the cyclohexene ring is epoxidised. It is of advantage to epoxidisewith the aid of an organic peracid, such as peracetic, perbenzoic,peradipic, monoperphthalic acid or a similar acid that attacks thecarbon-to-carbon double bond in the olefinic side chain only under muchmore drastic reaction conditions that it does the cycloolefinic doublebond.

In the course of the epoxidation there may be formedapart from themonoepoxides-by side reactions, also hydrolysed epoxides, that is to saycompounds in which the epoxide groups of the monoepoxide of the FormulaI have been hydrolysed to hydroxyl groups.

It has been discovered that the presence of such byproducts in general'has a favourable effect on the technical properties of the curedepoxides. As a rule, it is therefore of advantage not to isolate thepure monoepoxides from the reaction mixture.

Particularly easy to manufacture are, for example, the mono-epoxides ofthe formula in which R represents a hydrogen atom or a lower alkylradical, and X and X each represents a hydrogen atom or a methyl group.

In general, the monoepoxides of the invention are at room temperatureclear liquids of low viscosity.

Unexpectedly, and in contrast to known monoepoxides such as butylglycide, cresyl glycide, styrene oxide and the like, the products of theinvention can be crosslinked and cured with the conventional curingagents in the same manner as polyepoxides.

Suitable curing agents are basic or more especially acidic compounds.

The following have proved suitable as curing agents: Amines or amides,such as aliphatic and aromatic primary, secondary and tertiary amines,for example mono-, diand tributylamines, para-phenylenediamine,bis-[para-aminophenyl]-methane, ethylenediamine,NzN-diethyl-ethylenediamine, diethylenetriamine,tetra-[hydroxyethyl]-diethy1- enetriamine, triethylenetetramine,tetraethylenepentamine, N:N-dimethylpropylenediamine, trimethylamine,diethylamine, triethanolamine, Mannichs bases, piperidine, piperazine,guanidine and guanidine derivatives such as phenyldiguanidine,diphenylguanidine, dicyandiamide, aniline-formaldehyde resins,urea-formaldehyde resins, melamine-formaldehyde resins, polymers ofaminostyrenes, polyamides, for example those obtained by reactingaliphatic polyamines with dimerised or trimerised unsaturated fattyacids, isoeyanates, isothiocyanates; polyhydric phenols, for exampleresorcinol, hydroquinone, bis -[4- hydroxyphenyl]-dimethylmethane,quinone, phenol-aldehyde resins, oil-modified phenol-aldehyde resins,reaction products of aluminum alcoholates or phenolates with compoundsof tautomeric reaction of the type of acetoacetic esters, Friedel-Craftscatalysts, such as aluminum chloride, antimony pentachloride, tintetrachloride, zinc chloride or boron trifluoride or complexes thereofwith organic compounds; metal fluoborates, boroxines, or phosphoricacid. Preferred use is made as curing agents of polybasic carboxylicacids and anhydrides thereof, for example phthalic anhydride,methylendomethylene tetrahydrophthalic anhydride, dodecenyl-succinicanhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,hexachloroendomethylene tetrahydrophthalic anhydride or endomethylenetetrahydrophthalic anhydride, or mixtures of said anhydrides; maleic orsuccinic anhydride. If desired, there may be further added anaccelerator, such as a tertiary amine or a strong Lewis base, forexample an alkali metal alcoholate, and advantageously also polyhydroxycompounds such as hexanetriol, or glycerol.

It has been found that the new monoepoxides are advantageously curedwith carboxylic acid anhydrides in a concentration of 0.3 to 0.9 gramequivalent of anhydride groups per gram equivalent of epoxide groups.

When a basic accelerator is used, such as an alkali metal alcoholate oralkali metal salt of a carboxylic acid, up to 1.0 gram equivalent ofanhydride groups may be used.

The most important use of the monoepoxides of the invention lies intheir mixture with curable polyepoxides or epoxy resins, especially asactive diluents. The addition of a so-called active diluent is oftendesirable in casting or laminating resins or solvent-free lacquers toproduce curable resin mixtures of as low a viscosity as possible thatare liquid at room temperature. All known active diluents for epoxyresins such, for example, as cresyl glycide, have the seriousshortcoming that they have an extremely unfavourable eit'ect on themechanical thermal stability of the cured resins. Most unexpectedly, .ithas now been observed that the monoepoxides of the invention constituteexcellent active diluents by virtue of their low viscosity and,moreover, they even enhance the mechanical thermal stability of thecured resin mixtures as a rule, or at least they reduce it as worst onlynegligibly.

As examples of diepoxide and polyepoxide compounds preferably usedtogether 'with the monoepoxides of the invention there may be mentioned:Epoxidised diolefines, dienes or cyclic dienes such as butadienedioxide, vinyl cyclohexene dioxide, 1:2:516-diepoxyhexane and 1:2:4z5-diepoxycyclohexane; epoxidised diolefinically unsaturated carboxylicacid esters, such as methyl-9:10:12zl3-diepoxystearate; the dimethylester of 6z7zl0 zll-diepoxyhexadecane-l l6-dicarboxylic acid; epoxidisedcompounds containing two cyclohexenyl groups, such as bis-[3:4-epoxy-cyclohexylmethyl]-succinate, bis-[3:4-epoxycyclohexylmethyl]-phthalate, diethyleneglycol bis [3:4-epoxy-cyclohexane-carboxylate], 3:4 epoxy-cyclohexylmethyl 3 :4 epoxycyclohexane carboxylate and 3:4- epoxy-'6-methylcyclohexylmethyl-3:4epoxy 6-methylcyclohexane-carboxylate. Furthermore basic polyepoxidessuch as are obtained by dehydrohalogenating reaction products of primaryor secondary amines, such as n-butylamine, aniline or4:4-di-[monomethylamino]-diphenyl methane, with epichlorohydrin. Furthersuitable are polyglycidyl esters such as are obtained by reacting adicarboxylic acid with epichlorohydrin. or dichlorohydrin in thepresence of alkali. Such polyesters may be derived from aliphaticdicarboxylic acids such as oxalic, succinic, glutaric, adipic, pimelic,suberic, azelaic, sebacic acid and more especially of aromaticdicarboxylic acids such as phthaljc, isophthalic, terephthalic,2:6-naphthylene-dicarboxylic acid, diphenyl-ortho:ortho'-dicarboxylicacid, or ethylene glycol-bis-(para-carboxyphenyl)-ether and the like.There may be mentioned, for example, diglycidyl adipate and diglycidylphthalate, as well as diglycidyl esters of the average formula such as aphenylene radical, and z is a small integer or fraction included, forexample, between and 2.

Further suitable are polyglycidyl ethers such as are obtained byetherifying a polyhydric alcohol or polyphenol with epichlorohydrin ordichlorohydrin in the presence of alkali. These compounds may be derivedfrom glycols, such as ethylene glycol, diethylene glycol, triethyleneglycol, 1:2-propanediol, lz3-propanediol, 1:4-butanediol,1:5-pentanediol, 1:6-hexanediol, 2:4:6-hexanetriol, glycerol and moreespecially polyphenols such as phenol and cresol novolaks, resorcinol,pyrocatechol, hydroquinone, l :4-dihydroxynaphthalene, bis-[4-hydroxyphenyl1-methane, bis-[4-hydroxyphenyl]-methylphenylmethane,bis- [4-hydroxyphenyl]-tolylmethane, 4:4'-dihydroxydiphenyl,bis-[4-hydroxyphenyl]-sulfone and above all 2:2-bis-[4-hydroxyphenyl]-propane (bisphenol). There may be mentioned ethyleneglycol diglycidyl ethers and resorcinol diglycidyl ethers, as well asdiglycidyl ethers of the average formula O CHI-CH in which X representsan aromatic hydrocarbon residue, such as the phenylene residue, or thehydrocarbon residue of bisphenol, and z represents a small integer orfraction included, for example, between 0 and 2.

Accordingly, the present invention further provides curable mixturescontaining a monoepoxide of the invention, preferably together with adiepoxide or polyepoxide, as well as a curing agent for epoxy resins,preferably an anhydride of a dicarboxylic or polycarboxylic acid.

The monoepoxides of the invention and their mixtures with polyepoxidesand/ or curing agents may further be mixed, at any stage prior to thecuring operation, with fillers, plasticisers, coloring matter or thelike. Suitable extenders and fillers are, for example, asphalt, bitumen,glass fibers, mica, quartz meal, cellulose, kaolin, finely distributedsilicic acid (AEROSIL) or metal powders.

The mixtures containing in addition to a monoepoxide of the invention apolyepoxide and/ or a curing agent can be used without or with a filler,if desired in the form of a solution or emulsion, as textile assistants,laminating resins, paints, lacquers, dipping resins, casting resins,coating compositions, pore fillers, putties, adhesives, mouldingcompositions and the like, as well as for the manufacture of suchsubstances. The new resins are of special importance when used asinsulating compounds for electrical purposes.

In the following examples parts and percentages are by Weight; therelationship between parts by Weight and parts by volume is the same asthat between the kilogram and the liter.

EXAMPLE 1 (A) Acetal from acrolein and 1:1-bis-[hydr0xymethyl]-cyclohexene-3 A mixture of 286 parts of l:l-bis[hydroxymethyl]-cyclohexene-3, 118 parts of acrolein and 3 parts of sulfuric acid of 50%strength is stirred and heated in an oil bath to an external temperatureof C., and after 30 minutes 350 parts by volume of benzene are addeddropwise. The oil bath temperature is then raised to 120- C. and thewater eliminated by the reaction is distilled 01f azeotropically withthe aid of a circulation distillation apparatus (see the publication byH. Bather and co-workers in Die Makromolekulare Chemie, Volume 7,[1951], pages 8485). After 2 hours the benzene is removed under reducedpressure. The residue (344 parts) is mixed with 1.5 parts of sodiumacetate and distilled in vacuo. The acetal (3-vinyl-2:4-dioxospiro 5 :5)-undecene-9) distills at 94-99 C. under a pressure of 6 mm. Hg.

Yield: 226 parts=62.5% of the theoretical. n =l.4908.

(B) 'Epoxidation 900 parts of the acetal prepared as described inExample 1(A) are dissolved in 2250 parts of benzene, treated with 100parts of sodium acetate, and 1045 parts of peracetic acid of 40%strength are carefully stirred in dropwise at 2530 C. After about 4hours 100% of the calculated amount of peracetic acid has undergonereaction. The whole is then agitated in a separating funnel 3 times with200 parts by volume of water and 4 times with 300 parts by 'volume ofsaturated sodium carbonate solution on each occasion, until an alkalinereaction has been established, dried over sodium sulfate and the benzeneis distilled oil under reduced pressure.

The epoxidised acetal (3-vinyl-2:4-dioxospiro(5:5)- 9:10-epoxy-undecane) of the formula passes over at 90 to 98 C. under apressure of 0.5 to 0.6 mm. Hg.

Yield: 739 parts=75.5% of the theoretical.

Epoxide content: 514 epoxide groups per kg. (theory:

5.1 epoxide groups per kg.).

Determination of double bonds: 6.0 double bonds per kg. (theory: 5.1double bonds per kg.).

The above monoepoxide (100 parts) can be cured with phthalic anhydride(46 parts) in the presence of 2:4- dihydroxy-3-hydroxymethyl-pentane (23parts) at 180 C. to yield a hard casting.

EXAMPLE 2 (A) Acetal from crotonic aldehyde and 1:1-bis-[hydroxymethyl]-cyclohexene-3 652 parts of the acetal prepared asdescribed in Example 2(A) are dissolved in 1680 parts by volume ofbenzene, treated with 70 parts of sodium acetate and epoxidised asdescribed in Example 1(B) at 2530 C. with 704 parts of peracetic acid of40% strength. The epoxidised acetal(3-propenyl-2:4-dioxospiro(5:5)-9:10- epoxy-undecane) of the formulaCHr-O /C xi passes over at 114-118 C. under a pressure of 0.6 to 0.8 mm.Hg.

Yield: 381 parts:54% of the theoretical.

Epoxide content: 4.65 epoxide groups per kg. (theory:

4.75 epoxide groups per kg.).

Determination of double bonds: 4.3 double bonds per kg. (theory: 4.75double bonds per kg.).

6 EXAMPLE 3 (A) Acetal from crotonic aldehyde and 1:l-bis-[hydroxymethyl] -6-methyl-cyclohexene-3 312 parts of1:l-bis-[hydroxymethyl]-6-methyl-cyclohexene-3 and 140 parts of crotonicaldehyde are condensed as described in Example 1(A) with addition of 1part of sulfuric acid of 50% strength and 350 parts by volume ofbenzene. The acetal (3-propenyl-7-methyl-2:4-dioxospiro(5:5)-undecene-9)passes over at 116134 under a pressure of 5 mm. Hg.

Yield: 243 parts=58.5% of the theoretical. n =1.4941. (B) Epoxidation832 parts of the acetal prepared as described in Example 3(A) aredissolved in 2500 parts by volume of benzene, treated with parts ofsodium acetate and epoxidised with 836 parts of peracetic acid of 40%strength at 25-30 C. as described in Example 1(B). The epoxidised acetal(3-propenyl-7-methyl-2:4-dioxospiro(5:5)- 9:10-epoxy-undecane) of theformula passes over at 103113 C. under a pressure of 0.2 mm. Hg.

Yield: 371 parts=45.5% of the theoretical. Epoxide content: 4.3 epoxidegroups per kg. (theory:

EXAMPLE 4 (A) Acetal from acrolein and 2:5-endomethy1ene-A cyclohexene-ll-dimethanol 154 parts of1:l-bis-[hydroxymethylJ-Z:S-endomethylenecyclohexene-3 are dissolvedwith stirring at an external temperature of 50 C. in 500 cc. of benzeneand treated in succession with 1 part each of zinc chloride andorthophosphoric acid and then with 59 parts of acrolein. The mixture isstirred for 20 minutes at 50 C. and then rapidly raised in a preheatedoil bath to an external temperature of 120 C., while distilling off thereaction water azeotropically with the aid of a circulation distillationapparatus (see the publication by H. Batzer and coworkers in DieMakromolekulare Chemie, vol. 7, [1951], pages 84-85). After about 1 hour18 parts of water have been separated in this manner. During thecooling, 15 parts of anhydrous sodium acetate are added, the whole isfiltered, and the benzene is removed in a circulation evaporator. Theslightly yellowish residue (210 parts) is distilled off under reducedpressure through a Vigreux column. The water-clear acetal passes over at9495 C. under a pressure of 0.5 mm. Hg.

Yield: 168.5 parts=87.5% of the theoretical.

Determination of double bonds: 10.02 (theory: 10.42)

double bonds per kg.

Analysis.C H O Molecular Weight 192.25. Found (percent): C, 75.30; H,8.38. Calculated (percent): C, 74.97; H, 8.39.

(B) Epoxidation A solution of 96 parts of the acetal prepared asdescribed in Example 1(A) in 300 parts of benzene is treated with 20parts of sodium acetate, and 100 parts of peracetic acid of 42% strengthare carefully stirred in dropwise at 3540 C. After about 50 minutes,102% of the calculated amount of peracetic acid has undergone reaction.The reaction mixture is then cooled to 20 C., shaken three times with 50parts of water and twice with 50 parts of saturated sodium carbonatesolution on each occasion, until an 7 alkaline reaction has beenestablished then dried over sodium sulfate, filtered, and the benzene isdistilled off under reduced pressure. Yield: 98 parts (=94% of thetheoretical) of a water-clear crude product containing 124% of doublebonds (calculated on monoepoxide) The monoepoxide of the formula passesover at 9699 C. under a pressure of 0.3 mm. Hg.

Yield: 68.5 parts=66% of the theoretical. n =1.5115. Determination ofdouble bonds: 4.4 double bonds (theory:

4.8) per kg.

Analysis.C H O Molecular weight 208.25. Found (percent): C, 69.5; H,7.92. Calculated (percent): C, 69.21; H, 7.74.

EXAMPLE 5 (A) Acetal from methacrolein and Aflcyclohexene- 1l-dimethanol 284 parts of 1:1-bis-[hydroxymethyl]-cyclohexene-3 aredissolved in 700 parts of benzene with stirring at an externaltemperature of 50 C. 2 parts each of zinc chloride and ortho-phosphoricacid and then 163 parts of methacrolein of 90% strength are added andthe whole is stirred for 20 minutes at 50 C., then rapidly raised to anexternal temperature of about 120 C. and the Water of reaction isdistilled off azeotropically with the aid of a circulation distillationapparatus. Within one hour 35.5 parts of Water are separated in thismanner. After cooling, parts of sodium acetate are added, the whole isfiltered and the benzene is removed under reduced pressure. The residue(388 parts) is distilled off in vacuo through a ing 4.75 epoxide groupsper kg. The rnonoepoxide of the formula passes over at 86 to 94 C. undera pressure of 0.8 mm. Hg.

Yield: 140 parts=67% of the theoretical. n Determination of epoxidegroups: 5.05 epoxide groups (theory: 474) per kg. Analysis.--C H OMolecular weight 210.26. Calculated (percent): C, 68.54; H, 8.63. Found(percent): C,68.33; H, 8.40.

EXAMPLE 6 Test specimens of a polyglycidyl ether resin which is solid atroom temperature and contains 2.55 epoxide equivalents per kg, preparedby reacting epichlorohydrin with bis-[4-hydroxyphenyl]-dimethylmethanein the presence of alkali (resin A), and test specimens of resinmixtures obtained by dissolving at about 70 C. a monoepoxide prepared asdescribed in Example 1 (monoepoxide D) in resin A, are melted withphthalic anhydride as curing agent at 120 -125 C., using in each caseper equivalent of epoxide groups of resin A and, respectvely, of theresin mixture A+D, 0.85 equivalent of anhydride groups.

Each mixture is cast at about 120 C. in an aluminum mould x 10 x 140mm.) and cured for 24 hours at 140 C.

The viscosity of the resin A and of the resin mixture A+D, the pot lifeof the resin+curing agent mixtures as well as the properties of thecured castings are shown in the following table:

Pot life Vigreux column. The acetal passes over at 54 to 58 C. under apressure of 0.1 mm. Hg.

Yield: 309 parts=80% of the theoretical. n. =1.4910.

Analysis.C H O Molecular weight 194.26. Found (percent): C, 74.46; H,9.31. Calculated (percent): C, 74.16; H, 9.34.

(B) Epoxidation- A solution of 194 parts of the acetal prepared asdescribed in Example 2(A) in 400 parts of benzene is treated with 40parts of sodium acetate and 215 parts of peracetic acid of 42% strengthare stirred in dropwise at 35 to 40 C. After 2% hours 102% of thecalculated amount of peracetic acid has been reacted. 1000 parts ofbenezene are added and the mixture is agitated three times With 150parts of water and twice with parts of saturated sodium carbonatesolution on each occasion, until an alkaline reaction has beenestablished. The benzene solution is once again washed with 100 parts ofWater, dried over sodium sulfate and filtered and the benzene is removedunder reduced pressure. Yield: 202 parts (=96% 1.75 parts of a sodiumalcoholate, prepared by dissolving 0.82 part of sodium metal at about120 C. in 100 parts of 2:4-dihydroxy-3-hydroxymethyl-pentane, aredissolved in 100 parts each of resin A described in Example 6 and of theresin mixture A+D described in Example 6 at about 70 C. (specimen 1)and, respectively, at about 50 (specimen 2) and at room temperature(specimen 3). In each case 1.0 equivalent of phthalic anhydride perequivalent of epoxide groups is fused in as curing agent at 125 C. Theresulting mixtures are cast at about 120 C. in aluminum moulds asdescribed in Example 6 5 and each casting is cured for 24 hours at C.The

of the theoretical) of a water-clear crude product contain- 75 resultingcured castings have the properties shown in the following table:

9 EXAMPLE 8 A polyglycidyl ether resin which is liquid at roomtemperature, has a viscosity of 12,000 cp., at 23 C. and con- 10 What isclaimed is: 1. A monoepoxide of the formula tains 5.5 epoxideequivalents per kg. and has been prepared by reacting epichlorohydrinwith bis-[4-hydroxy- C 'CHz-O phenyl]-dimethylmethane in the presence ofalkali (resin B) is mixed at room temperature in two different ratios Iwith a monoepoxide (monoepoxide D) prepared as de- 2- 2 scribed inExample 1. These mixtures are melted with C phthalic anhydride as curingagent at 120-125 C., using in each case 0.85 equivalent of anhydridegroups per equivalent of epoxide groups. 5 a

As described in Example 6, each resulting mixture is in which R R2 R R RR and R each re cast mi tubes a clued for 24 hours at 9 sent a men iberselected fr om the group consisting of The vrscosrtres of the resmmixtures and the properties of a hydrogen and lower alkyl having 1 to 4carbon atoms R1 the cured castings are shown in the followmg table: andR5 when taken t h represent methylene, and X Viscosity Thermal and Xeach are members selected from the group con- $2 3305; sisting ofhydrogen and methyl. B plus D Bending t Martens 2. A monoepoxide of theformula Resin B, Resin D, at 23 0., strength, DIN Speelmen parts partsincp. kgJmm. in C. CH, CH2 0 iIIIIIIIIIII 33 i3 1 1123 ii? iii c H O tCH2-O X1 X2 EXAMPLE 9 25 \l In Experiment 1 1.75 parts of the sodiumalcoholate described in Example 7 are dissolved at room temperature 2Slightly higher tertpmlure in 100 Parts of the in which R is a memberselected from the group conahphatlc dlepoxlde (dlepoxlde C) of theformula sisting of hydrogen and lower alkyl having 1 to 4 carbon CH2 0-2 atoms, and X and X each are members selected from C the groupconsisting of hydrogen and methyl. 3. The monoepoxide of the formula o ll CH20 o H H: GE: GE CH2 CH2O o 2 C 2 oh \C/ CHOH=CH2 containing 6.2equivalents of epoxide groups per kg.; in Experiment 2 in 100 parts of amixture of epoxides con- CH2 sisting of 80 parts of diepoxide C and 20parts of the monoepoxide compound described in Example 2, and in C 1Experiment 3 in 100 parts of a mixture of epoxides consisting of 80parts of diepoxide C and 20 parts of the The mOHOePQXIde of the formulamonoepoxide compound described in Example 3.

In each case the curing agent used is 1.0 equivalent of E GHPO phthalicacid anhydride per equivalent of epoxide groups, CH CHCH=0H, fused in at120-129 c. GHPO As described in Example 6 a first portion of eachmixture prepared in this manner is cast in aluminum moulds E ECTCHs andcured for 24 hours at 140 C., while a second por- 1 2 tion is used forcementing tests. For the latter purpose degreased and polished strips ofaluminum sheet marketed The monoepoxlde 0f the formula under the tradename Anticorodal B (170 x 25 x 1.5 CH CH 0 mm.; 10 mm. overlap) arecemented together and cured for 24 hours at 120 C. CH C CHCH=CHCH:

The viscosities of diepoxide C and of the epoxide mixl ture as well asthe properties of the cured castings and CH cemented aluminum strips areshown in the following 2 table: CH2

Viscosity of diepoxide Thermal C. and of stability the epoxide Impact tomixture bending Bending Martens $1188! at 23 C strength, strength, DINstreng in ep kgJcm. lrgJmm. in C. kg./mm.

6. The monoepoxide of the formula A third portion each of specimens 2and 3 is cast in CH2 C\ a layer about 0.1 mm. thick on glass plates andcured for 24 hours at 140 C. The resulting faultless, hard films Q 10112.0 prove stable on immersion for one hour at room tempera- HC CH:ture in,5 N-sulfuric acid, 5 N-sodium hydroxide solution, water, acetoneand chlorobenzene.

7. A compound of the formula wherein X is selected from the groupconsisting drogen and methyl.

II XX I. TOVAR, Assistant Examiner 5 US. Cl. X.R.

of hy- 260-2, 19, 45.7, 47, 59, 67.7, 71, 72.5, 78, 89.7

1. A MONOEPOXIDE OF THE FORMULA